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Polymers
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Spectroelectrochemistry of Electroactive Polymer Materials
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Spectroelectrochemistry of Electroactive Polymer Materials

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (25 April 2022) | Viewed by 15681

Special Issue Editors

Dr. Alexander Nekrasov

E-Mail Website
Guest Editor
Frumkin Institute of Physical Chemistry and Electrochemistry, RAS, Moscow, Russia
Interests: conducting polymers; polyaniline; polythiophene; polypyrrole; electropolymerization; spectroelectrochemistry; UV–Vis–NIR spectroscopy; Raman spectroscopy
Dr. Oxana Gribkova

E-Mail Website
Co-Guest Editor
Frumkin Institute of Physical Chemistry and Electrochemistry, RAS, Moscow, Russia
Interests: conductive polymers; spectroelectrochemistry; conductive composites

Special Issue Information

Dear Colleagues,

This Issue is devoted to the application of various spectroscopic techniques aimed to study the electronic and molecular structure of electroactive polymer materials and polymer-inorganic composites, as well as to elucidate the mechanisms of structural transformations in these materials during:

- Redox or acidic doping/dedoping;

- Color changes in electrochromic devices;

- Response to the presence of analytes in sensor devices;

- Charging/discharging in energy storage devices;

- Operation of photoelectrochemical energy conversion devices.

The techniques include, but are not limited to, electronic spectroscopy in UV, visible, and near-infrared ranges, infrared and Raman spectroscopy, electron spin resonance spectroscopy, X-ray photoelectron spectroscopy, as well as purely electrochemical techniques such as electrochemical impedance spectroscopy and electrochemical quartz crystal microbalance, including acoustic impedance spectroscopy.

Dr. Alexander Nekrasov
Dr. Oxana Gribkova
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • spectroelectrochemistry
  • UV–Vis–NIR spectroscopy
  • IR spectroscopy
  • Raman spectroscopy
  • ESR spectroscopy
  • XPS spectroscopy
  • electrochemical impedance electrochemical quartz crystal microbalance
  • electrochemical acoustic impedance

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Published Papers (5 papers)

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Research

11 pages, 1336 KiB  
Article
Birefringence of Thin Uniaxial Polymer Films Estimated Using the Light Polarization Ellipse
by Mihai Postolache, Dan Gheorghe Dimitriu, Cristina Delia Nechifor, Simona Condurache Bota, Valentina Closca and Dana Ortansa Dorohoi
Polymers 2022, 14(5), 1063; https://doi.org/10.3390/polym14051063 - 7 Mar 2022
Cited by 8 | Viewed by 2949
Abstract
A simple method for determining the linear birefringence of the thin layers based on the determination of the orientation of the polarization ellipse of totally polarized light is proposed and it is applied to PVA thin foils. Theoretical notions and the experimental procedure [...] Read more.
A simple method for determining the linear birefringence of the thin layers based on the determination of the orientation of the polarization ellipse of totally polarized light is proposed and it is applied to PVA thin foils. Theoretical notions and the experimental procedure are described. The linear birefringence of polymer thin foils with different degrees of stretching is determined and the applicability of the method is discussed. Full article
(This article belongs to the Special Issue Spectroelectrochemistry of Electroactive Polymer Materials)
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16 pages, 4427 KiB  
Article
Poly(3,4-ethylenedioxythiophene) Electrosynthesis in the Presence of Mixtures of Flexible-Chain and Rigid-Chain Polyelectrolytes
by Varvara Kabanova, Oxana Gribkova and Alexander Nekrasov
Polymers 2021, 13(22), 3866; https://doi.org/10.3390/polym13223866 - 9 Nov 2021
Cited by 10 | Viewed by 2286
Abstract
The electrochemical synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) was first carried out in the presence of mixtures of flexible-chain and rigid-chain polyacids and their Na-salts. Earlier on with the example of polyaniline, we have shown the non-additive effect of the rigid-chain component of polyacid mixtures [...] Read more.
The electrochemical synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) was first carried out in the presence of mixtures of flexible-chain and rigid-chain polyacids and their Na-salts. Earlier on with the example of polyaniline, we have shown the non-additive effect of the rigid-chain component of polyacid mixtures on the electrodeposition of polyaniline films, their morphology and spectroelectrochemical properties. In this study, we confirmed the non-additive effect and showed that such mixed PEDOT–polyelectrolyte films possess unique morphology, spectroelectrochemical and ammonia sensing properties. The electrosynthesis was carried out in potential cycling, galvanostatic and potentiostatic regimes and monitored by in situ UV–Vis spectroscopy. UV–Vis spectroelectrochemistry of the obtained PEDOT–polyelectrolyte films revealed the dominating influence of the rigid-chain polyacid on the electronic structure of the mixed complexes. The mixed PEDOT–polyacid films demonstrated the best ammonia sensing performance (in the range of 5 to 25 ppm) as compared to the films of individual PEDOT–polyelectrolyte films. Full article
(This article belongs to the Special Issue Spectroelectrochemistry of Electroactive Polymer Materials)
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19 pages, 2915 KiB  
Article
Exohedral Functionalization of Fullerene by Substituents Controlling of Molecular Organization for Spontaneous C60 Dimerization in Liquid Crystal Solutions and in a Bulk Controlled by a Potential
by Malgorzata Czichy, Alessia Colombo, Pawel Wagner, Patryk Janasik, Claudia Dragonetti, Rathinam Raja, David L. Officer and Leeyih Wang
Polymers 2021, 13(16), 2816; https://doi.org/10.3390/polym13162816 - 22 Aug 2021
Cited by 3 | Viewed by 2950
Abstract
A study was carried out on the possibility of orderly and spontaneous dimerization at room temperature of C60 cages in fullerene liquid crystal fullerene dyads (R-C60). For this purpose, dyads with a structural elements feature supporting π-stacking and Van der [...] Read more.
A study was carried out on the possibility of orderly and spontaneous dimerization at room temperature of C60 cages in fullerene liquid crystal fullerene dyads (R-C60). For this purpose, dyads with a structural elements feature supporting π-stacking and Van der Waals interactions were tested, due to the presence of terthiophene donors linked through an α-position or dodecyloxy chains. In addition, this possibility was also tested and compared to dyads with shorter substituents and the pristine C60. Research has shown that only in dyads with the features of liquid crystals, π-dimerization of C60 units occurs, which was verified by electrochemical and spectroelectrochemical (ESR) measurements. Cyclic voltammetry and differential voltammetry studies reveal π-dimerization in liquid crystal dyad solution even without the possibility of previous polymerization (cathodic or anodic) under conditions in the absence of irradiation and without the availability of reaction initiators, and even with the use of preliminary homogenization. These dyads undergo six sequential, one-electron reductions of π-dimer (R-C60···C60-R), where two electrons are added successively to each of the two fullerene cages and first form two radical anion system (R-C60)•−(R-C60)•− without pairing with the characteristics of two doublets. Similarly, the second reductions of π-dimer occur at potentials that are close to the reduction potential for the conversion to a system of two triplet dianions (R-C60)2−(R-C60)2−. Electron paramagnetic resonance spectra indicate a significant interaction between C60 cages. Interestingly, the strength of intermolecular bonds is so significant that it can overcome Coulombic repulsion, even with such highly charged particles as dianions and trianions. Such behavior has been revealed and studied so far only in covalently bonded C60 dimers. Full article
(This article belongs to the Special Issue Spectroelectrochemistry of Electroactive Polymer Materials)
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16 pages, 4661 KiB  
Article
A Novel Cobalt Metallopolymer with Redox-Matched Conjugated Organic Backbone via Electropolymerization of a Readily Available N4 Cobalt Complex
by Mikhail Karushev
Polymers 2021, 13(10), 1667; https://doi.org/10.3390/polym13101667 - 20 May 2021
Cited by 3 | Viewed by 2339
Abstract
Fast and reversible cobalt-centered redox reactions in metallopolymers are the key to using these materials in energy storage, electrocatalytic, and sensing applications. Metal-centered electrochemical activity can be enhanced via redox matching of the conjugated organic backbone and cobalt centers. In this study, we [...] Read more.
Fast and reversible cobalt-centered redox reactions in metallopolymers are the key to using these materials in energy storage, electrocatalytic, and sensing applications. Metal-centered electrochemical activity can be enhanced via redox matching of the conjugated organic backbone and cobalt centers. In this study, we present a novel approach to redox matching via modification of the cobalt coordination site: a conductive electrochemically active polymer was electro-synthesized from [Co(Amben)] complex (Amben = N,N′-bis(o-aminobenzylidene)ethylenediamine) for the first time. The poly-[Co(Amben)] films were investigated by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM), in situ UV-vis-NIR spectroelectrochemistry, and in situ conductance measurements between −0.9 and 1.3 V vs. Ag/Ag+. The polymer displayed multistep redox processes involving reversible transfer of the total of 1.25 electrons per repeat unit. The findings indicate consecutive formation of three redox states during reversible electrochemical oxidation of the polymer film, which were identified as benzidine radical cations, Co(III) ions, and benzidine di-cations. The Co(II)/Co(III) redox switching is retained in the thick polymer films because it occurs at potentials of high polymer conductivity due to the optimum redox matching of the Co(II)/Co(III) redox pair with the organic conjugated backbone. It makes poly-[Co(Amben)] suitable for various practical applications based on cobalt-mediated redox reactions. Full article
(This article belongs to the Special Issue Spectroelectrochemistry of Electroactive Polymer Materials)
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11 pages, 7303 KiB  
Article
Interfacial Doping Effects in Fluoropolymer-Tungsten Diselenide Composites Providing High-Performance P-Type Transistors
by Hyeonji Lee, Seongin Hong and Hocheon Yoo
Polymers 2021, 13(7), 1087; https://doi.org/10.3390/polym13071087 - 30 Mar 2021
Cited by 11 | Viewed by 4228
Abstract
In this study, we investigated the p-doping effects of a fluoropolymer, Cytop, on tungsten diselenides (WSe2). The hole current of the Cytop–WSe2 field-effect transistor (FET) was boosted by the C–F bonds of Cytop having a strong dipole moment, enabling increased [...] Read more.
In this study, we investigated the p-doping effects of a fluoropolymer, Cytop, on tungsten diselenides (WSe2). The hole current of the Cytop–WSe2 field-effect transistor (FET) was boosted by the C–F bonds of Cytop having a strong dipole moment, enabling increased hole accumulation. Analysis of the observed p-doping effects using atomic force microscopy (AFM) and Raman spectroscopy shed light on the doping mechanism. Moreover, Cytop reduces the electrical instability by preventing the adsorption of ambient molecules on the WSe2 surface. Annealing Cytop deposited on WSe2 eliminated the possible impurities associated with adsorbates (i.e., moisture and oxygen) that act as traps on the surface of WSe2. After thermal annealing, the Cytop–WSe2 FET afforded higher p-type conductivity and reduced hysteresis. The combination of the Cytop–WSe2 FET with annealing provides a promising method for obtaining high-performance WSe2 p-type transistors. Full article
(This article belongs to the Special Issue Spectroelectrochemistry of Electroactive Polymer Materials)
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